Conversion of SulfinolSM to BASFs aMDEA

Incitec Pivot has converted the carbon dioxide (CO2) removal system in its Gibson Island
ammonia plant from SulfinolSM to aMDEA in early 2007. SulfinolSM solution is a mixture of
DIPA (di-isopropanolamine), sulfolane (tetrahydrothiophene dioxide) and water. The SulfinolSM
system had been used for more than 35 years and a solvent change was needed to reduce ongoing
chemical costs of the ammonia plant.
The sequence of project implementation, challenges encountered in design, commissioning and
operation of BASFs aMDEA system (activated methyl di-ethanol amine) is explained in detail in
this paper.

Venkat Pattabathula, Incitec Pivot Ltd

Gibson Island, Brisbane, Australia
Dr. Torsten Katz
BASF East Asia Regional Headquarters Ltd., Hong Kong

replaced with a Hydro Agri (now Yara)

fluidised bed granulation unit in 1999.

Introduction

The plant is located at Gibson Island (GI) in the

suburbs of Brisbane City on the East Coast of
Australia.

ncitec Pivot operates an ammonia plant

originally of 600 mtpd, designed by J.F.
Pritchard, which has been upgraded to 800
mtpd over the years since its commissioning in
the late sixties. The unique features of this
ammonia plant are a low pressure (450 psig, 32
bar) front-end, a high-pressure back-end (2600
psig, 182 bar), a medium pressure steam system
(400 psig, 28 bar, 750 F, 400 C), a closed loop
refrigeration system and a jet engine that drives
a reaction turbine, which in turn drives the
synthesis gas (syngas) compressor. The site also
has a urea plant of Vulcan Cincinnati design,
which has also been upgraded over the years to
about 850 mtpd. The urea prilling section was

2007

Background
In ammonia plants, the carbon dioxide (CO2)
removal section is a key part of the ammonia
plant front-end where CO2 from process gas is
separated to provide more pure hydrogen (H2)
and nitrogen (N2) for the ammonia synthesis
reaction. The recovery of CO2 is also required
as a supply for the production of granular urea
and liquid CO2. The economics of the ammonia
plant heavily depends on the efficiency of

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AMMONIA TECHNICAL MANUAL

maintain its levels in the system. The SulfinolSM

system had been very reliable with corrosionfree operation ever since arsenic was added to
the system. Antifoam was also injected on a
needs basis to deal with foaming issues in the
CO2 stripper and absorber. The SulfinolSM
chemical makeup rates were quite high due to
degradation of the solution to oxazolidone and
the costs were on an increasing trend due to
higher chemical prices.

solvent systems used for the removal of CO2

from process gas. Over the last five decades,
there have been many industry innovations from
ordinary water wash to potassium solutions to
primary, secondary and tertiary amines.
The SulfinolSM CO2 removal solution consists of
sulfolane (tetrahydrothiophene dioxide) and
DIPA (di-isopropanol amine) up to a total
concentration of 65% in the system. SulfinolSM
was the preferred solvent when the Gibson
Island (GI) ammonia plant was built in the late
sixties.

Many SulfinolSM systems in natural gas plants

have changed over to aMDEA solvent for
capacity increases and reduced chemical costs.
The GI plant could be one of the few NH3
plants in the world operating with SulfinolSM.
Typical composition of SulfinolSM solution:
- DIPA: 50-55%; Sulfolane: 10-15%;
Oxazolidone: 10-15%; water: 20-25%.

The CO2 removal system at GI is a single stage

lean/rich solvent system (Figure 1) that consists
of major unit operations such as an absorber,
stripper and several heat exchangers. The lean
SulfinolSM solvent is fed to the CO2 absorber
where CO2 in process gas is absorbed in
SulfinolSM solution to produce CO2 rich
solution. The rich solution is sent to the CO2
stripper after exchanging heat with the lean
solution from the stripper in the lean/rich
solution exchangers.

aMDEA Process Simulation and

Design
BASF carried out an initial simulation of the
CO2 removal section.
The recommended
strength of aMDEA was 40 wt%. BASF
identified the need to replace the random
packing with structured packing in the CO2
stripper (D601), as it was very short (5 m or 17
ft) compared to their earlier plant retrofits.
Sulzer performed design checks on the stripper
internals and supplied the new internals.

A HP flash drum was installed as part of earlier

plant upgrade to remove inert gases from the
solution. The lean solution is further cooled
against cooling water (CW) where remaining
heat is removed. This additional heat load on the
cooling tower consumes a significant amount of
city water, which has special importance due to
water supply restrictions from Brisbane City
Council. The SulfinolSM solvent is circulated
between absorber and stripper by two parallel
pumps and a third pump is standing by.

Orica Engineering Services were involved in the

initial design checks and prepared engineering
specifications for the side stream filtration unit.

The ammonia plant has a SulfinolSM reclaimer

where degraded chemical product known as
oxazolidone is removed through vacuum
distillation and the sludge is used to coat a
product to suppress dust in the granulation plant.
About 6 tonnes per day of steam are used in the
reclaimer reboiler.

Lean solution pump (P604s) curves were

checked and found suitable for the aMDEA
conversion. The Stripper overhead reflux pump,
(P603s) curves were also checked & found to be
adequate, but new valve trim was required for
the stripper reflux drum (T604) level control
valve, LCV602A.

An arsenic based solution that acts as a

corrosion inhibitor is added on weekly basis to
AMMONIA TECHNICAL MANUAL

26

2007

feature that is required for this type of

solvent system. Since the new system
requires lower circulation rates with
aMDEA as compared with SulfinolSM,
most of the existing equipment was
adequate.
9. Corrosion coupons in rich & lean
solution lines.

BASF advised on the solvent piping stressrelieving requirements for aMDEA system.
Fortunately, no stress relieving measures were
required for using aMDEA.

Modifications to Existing
SulfinolSM System

No changes were made to the absorber

column and its internals already had SS
random packing.

The following changes were made to the CO2

stripper:
1. Replacement of current random packing
with high efficiency structured packing
(Figure 2) of Sulzer Mellapak to
increase mass transfer efficiency and
capacity.
a. Bottom 11 layers, Mellapak
170X for higher capacity (of that
3 layers thicker sheet material for
added strength).
b. Top 13 layers, Mellapak M2X
for higher efficiency.
2. Replacement of liquid downcomers with
envelope type downcomers for top wash
trays.
3. Replacement of the flash gallery (Figure
3) to conform to BASF design
requirements.
4. Replacement of the liquid distributor
(Figure 4) to improve liquid distribution
in the column.
5. New support grid (Figure 5) that is
suitable for structured packing.
6. Opening up of all bubble caps (Figure 6)
on the wash trays: some caps previously
had been blanked off.
7. Installation of stiffening plates (Figure
7) on two wash trays in order to prevent
any damage to the wash trays during
operation. This had become necessary,
as the distance between the flash gallery
and trays was only 300 mm versus an
optimum design of 500 mm.
8. A new side stream filtration unit and an
improved antifoam dosing system were
also installed as part of the project. The
side stream filtration is a common
2007

Risk Assessments and HAZOP Study

This project was justified based on the reduced
chemical costs, and savings from cooling water
and steam.
All phases of this project posed risk - design,
engineering
and
implementation.
Poor
implementation could have resulted in delays to
the plant start up due to the extension of the
post-2007 shutdown period. These risks were
minimised by the following:
- Choosing BASFs aMDEA process with
more than 200 plants in operation.
- The supplier of chemical plant internals for
absorption and desorption columns, Sulzer,
carried out design checks and also suggested
modifications suitable for the GI application.
Sulzer has been a main vendor for many of
BASFs designed plants & retrofit applications.
- Orica Engineering Shared Services (OESS)
reviewed the BASF and Sulzer designs, and all
other existing equipment. OESSs expertise in
the design review of the packed columns further
mitigated risks to the project.
- Design reviews, risk assessments and HAZOP
studies were carried out.

27

AMMONIA TECHNICAL MANUAL

All new internals for the CO2 stripper were

chemically cleaned prior to shutdown by
submerging them into a 3 wt% caustic solution
in a warmed-up bath outside the plant. The
purpose of the chemical cleaning is to remove
manufacturing oils, which are responsible for
foaming of the amine solution. After the
chemical cleaning, the internals were rinsed
with demin water and it was confirmed there
was no potential for foaming in the rinse water.

- Visits were made to existing ammonia plants

in the US and Western Australia that have
successfully changed over their SulfinolSM
systems to aMDEA. The long operating
experience gained at these plants was applied to
GI design and implementation.
- BASF provided classroom training to all shift
operating teams prior to shutdown where unit
operations of CO2 removal system were
discussed in detail.

The old internals such as flash gallery, liquid

distributor and SS random packing (raschig
rings) were removed and the vessel was
inspected. We observed heavy scale build up on
the CO2 stripper vessel walls and as much of it
as possible was removed within the maintenance
window by chipping it from the vessel. Then the
vessel was cleaned.

- Based on BASF information, a comprehensive

training package for the new aMDEA system
was developed for the ammonia plant operators.
- Incitec Pivot laboratory was supplied with new
analytical procedures by BASF and discussions
were held with BASF regarding tests for
aMDEA strength and foam.

Extensive scale build up was also noticed on the

bubble caps of stripper top wash trays and they
were sandblasted prior to reinstallation (Figures
8 and 9).

The Project schedule was as follows:

Capital approval:
May 2006
Detail design:
June 2006
Order material:
June 2006
Delivery of material: December 2006
Installation & Commissioning:
February/March 2007.

The tube bundles of process gas reboilers,

E602A/B were removed and hydro blasted and
the shells, which had SulfinolSM sludge deposits,
were flushed with demin water.

Pre-Commissioning/
Commissioning

Also inspected were the CO2 absorber (D602),

vapour lines from E602s/E678, tube sheets of
solvent/solvent exchangers (E604s) and D601
solution outlet lines.

During shutting down of the plant, all the

SulfinolSM solution was transferred to its storage
tank, T605. Then, the system was flushed with
condensate (demin water) by circulating with
the lean solution pumps. First wash water was
recovered to use it in another plant and 2nd wash
water that had very low levels of SulfinolSM was
drained to plant effluent system. To insure that
hydrogen was removed from the SulfinolSM
solution, the solution was regenerated by using
the auxiliary steam reboiler prior to draining to
storage tank.

AMMONIA TECHNICAL MANUAL

Old packing support clips were removed and

new shims were provided prior to the
installation of new internals.
New internals were installed in the CO2 stripper
under the supervision of a Sulzer field engineer.
This took about a week.
Once the unit was handed back from
maintenance, the system was flushed with
demin water twice to ensure that suspended

28

2007

antifoam than was originally anticipated.

Overall, there are more benefits than originally
envisaged from this change to aMDEA, such
as reduced solvent circulation rates, lower
regeneration heat load and reduced heat
rejection to cooling tower.

solids & iron levels were within BASF

recommendations.
For commissioning, the system demin water
was first added to the system and circulation
was established after pressuring the CO2
absorber with nitrogen. Then aMDEA was
added to the water and solvent circulation was
established in early March 2007, well ahead of
gas introduction to the CO2 absorber while the
reformer and shift converters were being heated
up. Finally, process gas was introduced to the
absorber and the entire aMDEA system was
run for a week at reduced gas rates during
synthesis converter catalyst reduction.

N2 blanketing system
A new nitrogen blanketing system (Figure 10)
was installed on aMDEA solution storage tank,
as it was not there on the original SulfinolSM
solution tank. As part of this, a pressure
regulator in the N2 supply line, a pressure relief
coupled with vacuum breaker and a rupture disc
in the old tank vent line were installed (Figure
10). The anchor plates of the tank foundation
were reinforced with additional supports and
this has helped to improve tank safety and
integrity.

The side stream filter was first commissioned

with 20-micron polypropylene cartridge filters
and then switched to 5-micron filters. About 10
litres of antifoam were injected to the system as
an initial charge prior to gas feed.

Operating procedures were also modified to

ensure that, during plant outages, only lean
aMDEA is transferred to the storage tank after
regeneration of solution.

Operating Experience
The ammonia plant was initially operated at 600
mtpd until all the catalysts were reduced. No
issues were observed with the aMDEA system.
Plant rates were then raised to 740 mtpd for few
days where the system was steady and finally,
the plant rates were raised to a maximum of
860-865 mtpd.

Summary

At about 860 mtpd carryover of aMDEA

solution was experienced from the CO2 stripper
into the top reflux drum and then into the urea
plant. It was brought under control by dosing
antifoam. Initially, it was necessary to dose
antifoam almost every 2 hours. The system
strength was about 38% and it was brought up
to 40% by adding more aMDEA. We then
started isolating the side stream filter during the
dosing of antifoam. Both these conditions
helped us to reduce foaming.

Overall, the aMDEA system has been fairly

steady except for the need to dose slightly more
2007

29

SulfinolSM conversion to aMDEA was a

successful project that helped to reduce
operating costs of the Gibson Island
ammonia plant.
Significant energy savings were achieved by
not using the 2 bar (30psig) steam auxiliary
reboiler (E678), and by complete isolation
of the old SulfinolSM reclaimer system that
consisted of a steam reboiler, condenser and
sludge handling system.
Handling of heavy metals such as arsenic
based corrosion inhibitors have been
discontinued with aMDEA, as the system
no longer requires a corrosion inhibitor.
The water make up to the CO2 removal
section was reduced from 2 Tonnes/hr to
0.75 Tonnes/hr.
AMMONIA TECHNICAL MANUAL

new system has paid off well. There were no

major hiccups after change over of the
solvent.

The previous very frequent manual handling

of chemical drums is no longer required.
The aMDEA makeup requirements are
quite negligible in comparison to the
SulfinolSM system.
The aMDEA solvent circulation rates were
reduced by about 25% v/s SulfinolSM and
hence, there are energy savings from
reduced heat load on the cooling tower and
also from the lean solvent pumps.
The CO2 removal system with aMDEA
will allow us to operate the plant as high as
900 mtpd provided we dont have any other
constraints in the plant. This will be a
significant benefit for the long-term
operation of the plant.
A systematic approach to process design,
risk assessments, design reviews, hazop
study, shutdown plans for the installation of
new internals in the CO2 stripper, reference
plant visits, operator training, precommissioning and commissioning of the

Table 1.

AuthorsAcknowledgment
The authors acknowledge the support provided
by Agrium Kenai Nitrogen Operations (Bill
Switzer etal), Alaska for having shared their
experience in converting SulfinolSM to
aMDEA.
Also thanks is given to Yaso Vesely and Terry
Moses of Sulzer, Govind Mudaliar of Orica, GI
ammonia plant operations, the maintenance,
project engineering and laboratory teams, and
GI 2007 Shutdown team, who were involved in
the successful completion of this project from
conceptual stage to commissioning.

Physical properties SulfinolSM v/s aMDEA

pH:
Density, gm/ml
Viscosity, cP
Boiling point
of water free amine
mixture, C ( o F)
Combustible
Flammable

SulfinolSM
10.7
1.064
92

aMDEA
10.1
1.055
6.4

285 (545)
No
No

247 (477)
No
No

AMMONIA TECHNICAL MANUAL

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2007

Table 2. Operating conditions SulfinolSM v/s aMDEA

SulfinolSM
aMDEA
Production mtpd
820
860
Lean solvent
Circulation flow,
705
535
Tonnes/hr
Lbs per hour x 1000
1,554.5
1,179.6
CO2 stripper, D601
Overhead temp, C (F)

87 (188)

77 (170)

CO2 slip ppm, D602

200

130

CO2 stripper, D601

Reflux flow, Tonnes/hr

5.5

Water make up to
aMDEA system,
Tonnes/hr

0.75

Regeneration heat load

GJ/hr (BTU/hr)

121 (114)

92 (87)

2007

31

AMMONIA TECHNICAL MANUAL

Flash Gas Acid Off-Gas

Treated Gas

Condenser
E-606

Make-Up
Water

Lean Solution
Cooler
E-605 A/B

hp flash
C4

Absorber
C1

Stripper
C9

Reboiler
E-602 A/B E-678

Feedgas

E-604 C/D/E/F

Lean Solution
Pump

Solvent/Solvent
Heat Exchanger
E-604 A/B

Figure 1: Flow sheet of CO2 removal system

Figure 2. New structured packing and locating grid

AMMONIA TECHNICAL MANUAL

32

2007

Figure 3. New flash gallery

Figure 4. New liquid distributor in CO2 stripper

2007

33

AMMONIA TECHNICAL MANUAL

Figure 5. New support grid for packing in stripper

Figure 6. Wash tray on top of CO2 stripper

AMMONIA TECHNICAL MANUAL

34

2007

Figure 7. New stiffening plates on the bottom of wash trays

Figure 8. Scale build up on old bubble caps from old trays

2007

35

AMMONIA TECHNICAL MANUAL

Figure 9. Bubble caps after sand blasting

Figure 10. Nitrogen blanketing system for aMDEA storage tank

AMMONIA TECHNICAL MANUAL

36

2007